CN1254323A - Process for preparation of synthesis gas - Google Patents
Process for preparation of synthesis gas Download PDFInfo
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- CN1254323A CN1254323A CN98804035A CN98804035A CN1254323A CN 1254323 A CN1254323 A CN 1254323A CN 98804035 A CN98804035 A CN 98804035A CN 98804035 A CN98804035 A CN 98804035A CN 1254323 A CN1254323 A CN 1254323A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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- C01B32/40—Carbon monoxide
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A process for preparing a synthesis gas by reacting a carbon-containing organic compound with CO2 and/or steam, wherein use is made of a catalyst having carbon precipitation activity regulated to a very low value. The catalyst comprises a carrier made of a metal oxide and, supported thereon, at least one catalyst metal selected from among rhodium, luthenium, iridium, palladium, and platinum, and is characterized in that the specific surface area of the catalyst is not more than 25 m<2>/g, that the electronegativity of the metal ion in the carrier metal oxide is not more than 13.0, and that the amount of the catalyst metal carried is 0.0005 to 0.1% by mole in terms of metal based on the carrier metal oxide.
Description
Technical field:
The present invention relates to prepare the method for synthetic gas.
Background technology:
Synthetic gas is the mixed gas that contains hydrogen and carbon monoxide, is widely used in synthetic ammonia as raw material, methyl alcohol, acetic acid etc.
Such synthetic gas can react in the presence of catalyzer by hydrocarbon and steam and/or carbonic acid gas and prepare.But, in this reaction, the reaction of side reaction carbon laydown takes place, cause carbon laydown, and the problem that carbon laydown brings is to make poisoning of catalyst.
The raw material of carbon laydown is the CO that is used as the carbon containing organic compound of raw material and generates on the spot.Along with the rising of these raw material dividing potential drops, quickened the carbon laydown reaction.Therefore,, reduce reaction pressure simultaneously, can reduce the amount of carbon laydown by increasing the inlet amount of steam and carbonic acid gas.But in this case, need excessive use steam and carbonic acid gas,, bring the deficiency of several respects so again to reduce the dividing potential drop of carbon containing organic compound and CO.For example, pre-hot steam and the consumption of carbonic acid gas necessary energy increase.And the expense of separating these gases from product increases.In addition, because require big reaction unit, plant investment increases.
JP-A-5-208801 discloses a kind of carbonic acid gas conversion catalyst, contains the group VIII metal, loads on high purity, the ultra-fine magnesium oxide single crystal.JP-A-6-279003 discloses a kind of carbonic acid gas conversion catalyst, contains the ruthenium compound that loads on the carrier, and this carrier contains at least a alkaline earth metal oxide and aluminum oxide.JP-A-9-168740 discloses a kind of carbonic acid gas conversion catalyst that contains rhodium, loads on the carrier of II-IV family metal oxide or lanthanide metal oxide formation, or on the complex carrier of above-mentioned metal oxide and aluminum oxide formation.Use the reaction experiment of these catalyzer under environmental stress, to carry out.Under for the very important high pressure of industrial application, these catalyzer show high carbon laydown activity, are unsafty as the industrial application catalyzer therefore.
The objective of the invention is:
(1) provides a kind of by carbon containing organic compound and steam and/or carbon dioxide reaction
The method for preparing synthetic gas, this method can solve the carbon laydown problem;
(2) provide a kind of synthesis gas preparation method of above-mentioned form, wherein use a kind ofly to have
The active catalyzer of carbon laydown that suppresses.
Can understand other purpose of the present invention the narration below this specification sheets.Summary of the invention:
The inventor has realized above-mentioned purpose, thereby has finished the present invention through further investigation.
According to the present invention, a kind of method for preparing synthetic gas is provided, wherein in the presence of a kind of catalyzer, carbon containing organic compound and steam and/or carbon dioxide reaction is characterized in that, described catalyzer comprises the carrier that a kind of metal oxide forms, and selected from rhodium, ruthenium, iridium, in palladium and the platinum at least load on catalytic metal on the described carrier in the lump; The specific surface area of described catalyzer is 25m
2/ g or littler; The metal ion electronegativity of described carrier metal oxide is 13.0 or lower; And the amount of described catalytic metal based on described carrier metal oxide, is 0.0005-0.1 mole % in metal.
Catalyzer used in this invention (being also referred to as catalyzer of the present invention later on) contains selected from rhodium (Rh), ruthenium (Ru), and iridium (Ir), one of at least catalytic metal in palladium (Pd) and the platinum (Pt), and load on the carrier metal oxide with property.In this case, catalytic metal can be with metallic state or with metallic compound, and for example the form of oxide compound is carried out load.
Catalyzer of the present invention is characterised in that catalyzer has the carbon containing of making organic compound and is converted into the desired activity of synthetic gas, demonstrates remarkable inhibition side reaction simultaneously, i.e. the function of carbon laydown reaction.
Catalyzer used in this invention can significantly suppress the carbon laydown reaction, it is characterized in that:
(i) the metal ion electronegativity of carrier metal oxide is 13.0 or lower;
(ii) the specific surface area of catalyzer is 25m
2/ g or littler; With
(ii i) based on carrier metal oxide, the amount of the catalytic metal of load is 0.0005-0.1 mole %.
This catalyzer that the carbon laydown reactive behavior is had a very big inhibition is that the inventor finds first.
Metal oxide as carrier can be single metal oxide, or the compound metal oxide.In the present invention, the electronegativity of the metal ion on the carrier metal oxide is 13 or lower, preferred 12 or lower, more preferably 10 or lower.Lower bound is about 4.Like this, the electronegativity of the metal ion on the carrier metal oxide used in this invention is 4-13, preferred 4-12.The electronegativity of the metal ion on the metal oxide preferably is no more than 13, because the carbon laydown reaction can significantly take place.
The electronegativity of the metal ion on the metal oxide is defined as following formula:
Xi=(1+2i) Xo is wherein: Xi: the electronegativity of metal ion
Xo: the electronegativity of metal
I: electricity price number.
When metal oxide is complex metal oxides, use the average electrical negativity of metal ion.This mean value is to be included in the electronegativity of the every metal ion species in the complex metal oxides and the long-pending summation of the molar fraction of corresponding metal oxide in complex metal oxides.
The electronegativity of metal (Xo) is according to the definition of Pauling.The Pauling electronegativity is seen " FUJISHIRO, Ryoichi translates for W.J.Moore Physical Chemistry, Vol.1 ", 4
ThEdition, Tokyo Kagaku Dojin, p.707 (1974), Table 15.4.
The electronegativity of the metal ion on the metal oxide for example is described in detail in " Shokubaikoza, vol.2, p145 (1985), edited by Catalyst Societyof Japan ".
Metal oxide can comprise that those contain a kind of metal oxide of or at least two kinds of metals, and metal for example is Mg, Ca, Ba, Zn, Al, Zr and La.This quasi-metal oxides as an example is a single metal oxides, magnesium oxide (MgO) for example, calcium oxide (CaO), barium oxide (BaO), zinc oxide (ZnO), aluminum oxide (Al
2O
3), zirconium white (ZrO
2), and lanthanum trioxide (La
2O
3), and complex metal oxides, MgO/CaO for example, MgO/BaO, MgO/ZnO, MgO/Al
2O
3, MgO/ZrO
2, CaO/BaO, CaO/ZnO, CaO/Al
2O
3, CaO/ZrO
2, BaO/ZnO, BaO/Al
2O
3, BaO/ZrO
2, ZnO/Al
2O
3, ZnO/ZrO
2, Al
2O
3/ ZrO
2, La
2O
3/ MgO, La
2O
3/ Al
2O
3, and La
2O
3/ CaO.
Specific surface area used in this invention is 25m
2/ g or littler catalyzer can be by before the supported catalyst metals, at 300-1, and 300 ℃, preferably at 650-1,200 ℃ of following calcinated support metal oxides and obtaining.Behind catalytic metal in the load, this load the carrier of catalytic metal further at 600-1,300 ℃, preferably at 650-1,200 ℃ of calcinings down.Also can then at 600-1,300 ℃,, calcine this catalytic metal load product down, obtain catalyzer for 200 ℃ by catalytic metal is loaded on the carrier metal oxide preferably at 650-1.The upper limit of calcining temperature has no particular limits, but be generally 1,500 ℃ or lower, preferred 1,300 ℃ or lower.In this case, the specific surface area of catalyzer or carrier metal oxide can be controlled by calcining temperature and calcination time.
The specific surface area of catalyzer used in this invention or carrier metal oxide is preferably 20m
2/ g or littler, more preferably 15m
2/ g or littler most preferably is 10m
2/ g or littler.The lower limit of specific surface area is about 0.01m
2/ g.By specifying catalyzer, or wherein the electronegativity of metal ion be 13 or the specific surface area of lower carrier metal oxide in above-mentioned scope, can significantly suppress the carbon laydown activity of catalyzer.
Based on carrier metal oxide, in metal, the amount that loads on the catalytic metal on the carrier metal oxide is at least 0.0005 mole of %, preferably is at least 0.001 mole of %, more preferably is at least 0.002 mole of %.The upper limit is generally 0.1 mole of %, preferred 0.09 mole of %.In the present invention, the expectation of the amount of the metal of load is 0.0005-0.1 mole %, preferred 0.001-0.1 mole %.
In catalyzer of the present invention, the specific surface area of the catalyzer specific surface area with carrier metal oxide basically is identical.Like this, in this manual, the term of use " specific surface area of catalyzer " is identical with " specific surface area of its carrier metal oxide " implication.
The term of mentioning at this specification sheets that relates to catalyzer or carrier metal oxide " specific surface area " is with " BET method ", and " SA-100 " survey meter that uses Shibata Science Inc. to make records under 15 ℃ of temperature.
Catalyzer used in this invention has little specific surface area, and contains supported catalyst metal very in a small amount, has so extremely suppressed its carbon laydown reactive behavior.Yet this catalyzer has gratifying activity for carbon containing organic compound feedstock conversion is become synthetic gas.
Catalyzer used in this invention can prepare with traditional method.A kind of preferable methods of preparation catalyzer of the present invention is a pickling process.In order to adopt dipping method to prepare catalyzer of the present invention, a kind of catalyst metal salts or its aqueous solution are joined in the water dispersion that contains carrier metal oxide, and make it mixed.From the aqueous solution, isolate carrier metal oxide then, carry out drying and calcining then.Another kind method (early stage humidity method) also is effectively, wherein a kind of metal salt solution corresponding to the pore volume amount is joined in the carrier metal oxide bit by bit, with the surface of wetting this carrier equably, carries out drying and calcining then.In these methods, catalyst metal salts is used water miscible salt.Such water-soluble salt can be an inorganic acid salt, for example nitrate or hydrochloride, or organic acid salt, for example acetate or oxalate.As a kind of can the alternate method, metal acetylacetonates etc. can be dissolved in organic solvent, for example in the acetone, and with this solution impregnation on carrier metal oxide.When using the aqueous solution metal oxide-impregnated of catalytic metal salt, the exsiccant temperature is 100-200 ℃, preferred 100-150 ℃.When with an organic solvent flooding, the exsiccant temperature is than the high 50-100 of boiling point ℃ of described solvent.The incinerating temperature and time is suitably selected according to the specific surface area (specific surface area of catalyzer) of carrier metal oxide or the catalyzer that obtains.Normally used calcining temperature is 500-1,100 ℃.
In catalyst preparation process of the present invention,, can be the product that metal oxide that is purchased by calcining or the metal hydroxides that is purchased obtain as the metal oxide of carrier.The purity of metal oxide is at least 98% (weight), preferably is at least 99% (weight).But, can improve the active component of carbon laydown, the perhaps component of under reductive condition, decomposing, for example metal such as iron and nickel and silicon-dioxide do not wish to use.This class impurity in metal oxide wishes to be not more than 1% (weight), preferably is not more than 0.1% (weight).
Catalyzer of the present invention can use with various forms, and is for example Powdered, granular, spherical, column and cylindric.Can be according to the form of the suitable selecting catalyst of employed catalytic bed system.
Prepare synthetic gas according to the present invention, can be by making the carbon containing organic compound, with steam and/or carbonic acid gas, reaction in the presence of above-mentioned catalyzer and realizing.As the carbon containing organic compound, can use lower hydrocarbon, methane for example, ethane, propane, butane, or petroleum naphtha, or non-hydrocarbon compound, for example methyl alcohol or dme.The preferred methane that uses.In the present invention, advantageously use the Sweet natural gas (methane gas) that contains carbonic acid gas.
If the method for methane and carbon dioxide reaction (transforming with carbonic acid gas), this reaction is as follows:
If the method for methane and steam reaction (using steam reforming), this reaction is as follows:
In with the carbonic acid gas conversion reaction, temperature of reaction is 500-1,200 ℃, and preferred 600-1,000 ℃, reaction pressure is 5-40kg/cm
2The elevated pressure of G, preferred 5-30kg/cm
2G.When adopting the packed bed system to finish reaction, the air speed of gas (GHSV) is 1,000-10,000hr
-1, preferred 2,000-8,000hr
-1With respect to the carbon of every mole of starting compound in the carbon containing organic compound raw material, the amount of the carbonic acid gas that uses is the 20-0.5 mole, preferred 10-1 mole.
In using steam reforming reaction, temperature of reaction is 600-1,200 ℃, and preferred 600-1,000 ℃, reaction pressure is 1-40kg/cm
2The elevated pressure of G, preferred 5-30kg/cm
2G.When adopting the packed bed system to finish reaction, the air speed of gas (GHSV) is 1,000-10,000hr
-1, preferred 2,000-8,000hr
-1With respect to the carbon of every mole of starting compound in the carbon containing organic compound raw material, the amount of the steam that uses is the 0.5-5 mole, preferred 1-2 mole, more preferably 1-1.5 mole.
According to the present invention, with in the steam reforming process, can produce synthetic gas in a kind of industrial favourable mode, suppress carbon laydown simultaneously, remain on 2 moles in every mole of starting compound carbon or lower even work as the amount of steam.In view of every mole of starting compound carbon in traditional method requires the 2-5 mole steam, the present invention who uses 2 moles or lower quantity of steam just conversion reaction is steadily carried out has huge industrial value.
In the present invention, if prepare synthetic gas by the mixture reaction that makes carbon containing organic compound and steam and carbonic acid gas, the mixed ratio of steam and carbonic acid gas has no particular limits, but normally for example makes H
2O/CO
2Mol ratio be 0.1-10.
The inventive method can adopt various catalyst systems to carry out, packed bed system for example, fluidised bed system, suspension bed system and moving-bed system.
Embodiment:
To the present invention be described in further detail by embodiment below.Preparation of Catalyst embodiment 1
Aluminum oxide under 650 ℃, in air, calcine 1.5h (hour), its granular size is adjusted to 0.27-0.75mm.Then, with dipping method (incipient wetness method) Ru is loaded on the aluminum oxide.This product is further calcined down in 1,000 ℃ in air, obtains the Al of load Ru
2O
3(Ru content is 3.0 * 10 to catalyzer
-4G/g Al
2O
3,, be 0.03mol% in molar weight).By ruthenium chloride (III) aqueous solution is added drop-wise in the burnt aluminum oxide bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Ru concentration that is added drop-wise to ruthenium chloride (III) aqueous solution in the aluminum oxide is 0.05% (weight).This impreg in air in 120 ℃ of dry 2.5h, and under same atmosphere in 1,000 ℃ of calcining 1.5h, obtain the Al of load Ru
2O
3Catalyzer (surface-area: 18.6m
2/ g).Al
2O
3Al
3+Electronegativity Xi be 11.3.Preparation of Catalyst embodiment 2
Zirconium white is calcined 2h in air under 600 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Rh is loaded on the zirconium white.This product is further calcined down in 970 ℃ in air, obtains the ZrO of load Rh
2(Rh content is 8.4 * 10 to catalyzer
-6G/gZrO
2,, be 0.001mol% in molar weight).By acetic acid rhodium (III) aqueous solution is added drop-wise to burnt ZrO bit by bit
2In, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh concentration that is added drop-wise to acetic acid rhodium (III) aqueous solution in the zirconium white is 0.0065% (weight).This impreg in air in 120 ℃ of dry 2.5h, and under same atmosphere in 970 ℃ of calcining 2h, obtain the ZrO of load Rh
2Catalyzer (surface-area: 8.6m
2/ g).ZrO
2Zr
4+Electronegativity Xi be 12.0.Preparation of Catalyst embodiment 3
Magnesium oxide is calcined 2h in air under 600 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Rh is loaded on the magnesium oxide.This product further in air in 1,100 ℃ of down calcining, (Rh content is 2.6 * 10 to obtain the MgO catalyzer of load Rh
-3G/gMg in molar weight, is 0.1mol%).By acetic acid rhodium (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh concentration that is added drop-wise to acetic acid rhodium (III) aqueous solution in the magnesium oxide is 1.7% (weight).This impreg in air in 120 ℃ of dry 2.5h, and under same atmosphere in 1,100 ℃ of calcining 2h, obtain the MgO catalyzer (surface-area: 0.6m of load Rh
2/ g).The Mg of MgO
2+Electronegativity Xi be 6.6.Preparation of Catalyst embodiment 4
Use dipping method, Rh is loaded on (1/8 inch particulate form) on the magnesium oxide, in air, calcine 3h in 1,100 ℃.This product further in air in 400 ℃ of down calcinings, (Rh content is 1.5 * 10 to obtain the MgO catalyzer of load Rh
-3G/gMgO in molar weight, is 0.06mol%).By burnt MgO particle being immersed in 3h in acetic acid rhodium (III) aqueous solution that Rh concentration is 1.0% (weight), obtain above-mentioned impreg.Then this impreg in air in 120 ℃ of dry 2.5h, and under same atmosphere in 400 ℃ of calcining 3h, obtain the MgO catalyzer (surface-area: 0.7m of load Rh
2/ g).The Mg of MgO
2+Electronegativity Xi be 6.6.Preparation of Catalyst embodiment 5
Use dipping method, Rh is loaded on (1/8 inch particulate form) on the magnesium oxide, in air, calcine 3h in 1,100 ℃.This product further in air in 1,000 ℃ of down calcining, (Rh content is 2.6 * 10 to obtain the MgO catalyzer of load Rh
-5G/gMgO in molar weight, is 0.001mol%).By burnt MgO particle being immersed in 3h in the acetone soln of acetylacetonate rhodium (III) that Rh concentration is 0.017% (weight), obtain above-mentioned impreg.Then this impreg in air in 120 ℃ of dry 2.5h, and under same atmosphere in 1,000 ℃ of calcining 3h, obtain the MgO catalyzer (surface-area: 0.6m of load Rh
2/ g).The Mg of MgO
2+Electronegativity Xi be 6.6.Preparation of Catalyst embodiment 6
Use dipping method, Rh is loaded on (1/8 inch particulate form) on the magnesium oxide that contains the 5mol% calcium oxide, and in air, calcine 3h in 1,100 ℃.This product further in air in 950 ℃ of down calcinings, (Rh content is 7.5 * 10 to obtain the CaO/MgO catalyzer of load Rh
-4G/g (CaO/MgO) in molar weight, is 0.03mol).By burnt CaO/MgO particle being immersed in 3h in acetic acid rhodium (III) aqueous solution that Rh concentration is 0.5% (weight), obtain above-mentioned impreg.Then this impreg in air in 120 ℃ of dry 2.5h, and under same atmosphere in 950 ℃ of calcining 3h, obtain the CaO/MgO catalyzer (surface-area: 0.8m of load Rh
2/ g).The average electrical negativity Xi of the metal ion of carrier is 6.5.Preparation of Catalyst embodiment 7
Use dipping method, Rh is loaded on (1/8 inch particulate form) on the magnesium oxide that contains the 10mol% lanthanum trioxide, and in air, calcine 3h in 1,100 ℃.This product is further calcined down in 950 ℃ in air, obtains the La of load Rh
2O
3(Rh content is 9.0 * 10 to/MgO catalyzer
-5G/g (La
2O
3/ MgO),, be 0.006mol%) in molar weight.By with burnt La
2O
3/ MgO particle is immersed in 3h in the acetone soln of acetylacetonate rhodium (III) that Rh concentration is 0.1% (weight), obtains above-mentioned impreg.Then this impreg in air in 120 ℃ of dry 2.5h, and under same atmosphere in 950 ℃ of calcining 3h, obtain the La of load Rh
2O
3/ MgO catalyzer (surface-area: 0.8m
2/ g).The average electrical negativity Xi of the metal ion of carrier is 6.7.Preparation of Catalyst embodiment 8
Magnesium oxide is calcined 1.5h in air under 1,000 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Rh is loaded on the magnesium oxide.This product further in air in 950 ℃ of down calcinings, (Rh content is 2.6 * 10 to obtain the MgO catalyzer of load Rh
-4G/gMgO in molar weight, is 0.01mol%).By acetic acid rhodium (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh concentration of acetic acid rhodium (III) aqueous solution is 0.17% (weight).The material that has flooded Rh in air in 120 ℃ of dry 2.5h, and under same atmosphere in 950 ℃ of calcining 1.5h, obtain the MgO catalyzer (surface-area: 5.8m of load Rh
2/ g).Preparation of Catalyst embodiment 9
Magnesium oxide is calcined 2h in air under 920 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Ru is loaded on the magnesium oxide.This product further in air in 920 ℃ of down calcinings, (Ru content is 1.5 * 10 to obtain the MgO catalyzer of load Ru
-3G/gMgO in molar weight, is 0.06mol%).By hydration ruthenium chloride (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Ru concentration of ruthenium chloride (III) aqueous solution is 1.0% (weight).The material that has flooded Ru in air in 120 ℃ of dry 2.5h, and under same atmosphere in 920 ℃ of calcining 2h, obtain the MgO catalyzer (surface-area: 9.6m of load Ru
2/ g).Preparation of Catalyst embodiment 10
Magnesium oxide is calcined 3h in air under 300 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Ir is loaded on the magnesium oxide.This product further in air in 600 ℃ of down calcinings, (Ir content is 4.8 * 10 to obtain the MgO catalyzer of load Ir
-3G/gMgO in molar weight, is 0.10mol%).By iridium chloride (IV) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Ir concentration of iridium chloride (IV) aqueous solution is 3.2% (weight).The material that has flooded Ir in air in 120 ℃ of dry 2.5h, and under same atmosphere in 600 ℃ of calcining 3h, obtain the MgO catalyzer (surface-area: 24.8m of load Ir
2/ g).Preparation of Catalyst embodiment 11
Magnesium oxide is calcined 3h in air under 500 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Pt is loaded on the magnesium oxide.This product further in air in 750 ℃ of down calcinings, (Pt content is 4.8 * 10 to obtain the MgO catalyzer of supporting Pt
-3G/gMgO in molar weight, is 0.10mol%).By with Platinic chloride ([H
2PtCl
6]) aqueous solution is added drop-wise among the burnt MgO bit by bit, rocks after each drips and makes it mixed adding, and obtains above-mentioned impreg like this.The Pt concentration of chloroplatinic acid aqueous solution is 3.2% (weight).The material that has flooded Pt in air in 120 ℃ of dry 2.5h, and under same atmosphere in 750 ℃ of calcining 3h, obtain the MgO catalyzer (surface-area: 18.4m of supporting Pt
2/ g).Preparation of Catalyst embodiment 12
Magnesium oxide is calcined 3h in air under 300 ℃, its granular size is adjusted to 1.2-2.5mm.Then, with dipping method Rh is loaded on the magnesium oxide.This product further in air in 950 ℃ of down calcinings, (Rh content is 1.0 * 10 to obtain the MgO catalyzer of load Rh
-3G/gMgO in molar weight, is 0.04mol%).By acetic acid rhodium (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh concentration of acetic acid rhodium (III) aqueous solution is 0.68% (weight).The material that has flooded Rh in air in 120 ℃ of dry 2.5h, and under same atmosphere in 950 ℃ of calcining 3h, obtain the MgO catalyzer (surface-area: 6.0m of load Rh
2/ g).Preparation of Catalyst embodiment 13
Magnesium oxide is calcined 3h in air under 930 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Ru is loaded on the magnesium oxide.This product further in air in 970 ℃ of down calcinings, (Ru content is 7.5 * 10 to obtain the MgO catalyzer of load Ru
-4G/gMgO in molar weight, is 0.03mol%).By ruthenium chloride (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Ru concentration of ruthenium chloride (III) aqueous solution is 0.50% (weight).The material that has flooded Ru in air in 120 ℃ of dry 2.5h, and under same atmosphere in 970 ℃ of calcining 3h, obtain the MgO catalyzer (surface-area: 5.2m of load Ru
2/ g).Preparation of Catalyst embodiment 14
Magnesium oxide is calcined 3h in air under 350 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Rh is loaded on the magnesium oxide.This product further in air in 1,050 ℃ of down calcining, (Rh content is 2.0 * 10 to obtain the MgO catalyzer of load Rh
-3G/gMgO in molar weight, is 0.08mol%).By acetic acid rhodium (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh concentration of acetic acid rhodium (III) aqueous solution is 1.3% (weight).The material that has flooded Rh in air in 120 ℃ of dry 2.5h, and under same atmosphere in 1,050 ℃ of calcining 3h down, obtain the MgO catalyzer (surface-area: 1.5m of load Rh
2/ g).Preparation of Catalyst embodiment 15
Magnesium oxide is calcined 3h in air under 950 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Ru is loaded on the magnesium oxide.This product further in air in 950 ℃ of down calcinings, (Ru content is 2.5 * 10 to obtain the MgO catalyzer of load Ru
-4G/gMgO in molar weight, is 0.01mol%).Be added drop-wise to bit by bit among the burnt MgO by the aqueous solution, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this ruthenium chloride (III) hydrate.The Ru concentration of the aqueous solution of ruthenium chloride (III) hydrate is 0.17% (weight).The material that has flooded Ru in air in 120 ℃ of dry 2.5h, and under same atmosphere in 950 ℃ of calcining 3h, obtain the MgO catalyzer (surface-area: 4.8m of load Ru
2/ g).In this case, Ru is with the form load of ruthenium oxide.Preparation of Catalyst embodiment 16
Magnesium oxide is calcined 3h in air under 300 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Rh is loaded on the magnesium oxide.This product further in air in 1,050 ℃ of down calcining, (Rh content is 2.3 * 10 to obtain the MgO catalyzer of load Rh
-3G/gMgO in molar weight, is 0.09mol%).By acetic acid rhodium (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh concentration of acetic acid rhodium (III) aqueous solution is 1.5% (weight).The material that has flooded Rh in air in 120 ℃ of dry 2.5h, and under same atmosphere in 1,050 ℃ of calcining 3h down, obtain the MgO catalyzer (surface-area: 2.0m of load Rh
2/ g).In this case, Rh is with the form load of rhodium oxide.Preparation of Catalyst embodiment 17
Magnesium oxide is calcined 3h in air under 1,000 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Rh is loaded on the magnesium oxide.This product further in air in 950 ℃ of down calcinings, (Rh content is 1.5 * 10 to obtain the MgO catalyzer of load Rh
-4G/gMgO in molar weight, is 0.006mol%).By acetic acid rhodium (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh concentration of acetic acid rhodium (III) aqueous solution is 0.1% (weight).The material that has flooded Rh in air in 120 ℃ of dry 2.5h, and under same atmosphere in 950 ℃ of calcining 3h down, obtain the MgO catalyzer (surface-area: 5.6m of load Rh
2/ g).Preparation of Catalyst embodiment 18
Magnesium oxide is calcined 3h in air under 500 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Rh and Pt are loaded on the magnesium oxide.This product further in air in 1,050 ℃ of down calcining, (content of Rh and Pt is respectively 1.8 * 10 to obtain the MgO catalyzer of load Rh and Pt
-3G/gMgO and 4.8 * 10
-4G/gMgO, in molar weight, be respectively 0.07 and 0.01mol%).By with acetic acid rhodium (III) and Platinic chloride ([H
2PtCl
6]) the aqueous solution be added drop-wise to bit by bit among the burnt MgO, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh of this mixed water solution and the concentration of Pt are respectively 1.2% (weight) and 0.32% (weight).The material that has flooded Rh and Pt in air in 120 ℃ of dry 2.5h, and under same atmosphere in 1,050 ℃ of calcining 3h down, obtain the MgO catalyzer (surface-area: 1.4m of load Rh and Pt
2/ g).Preparation of Catalyst comparative example 1
Magnesium oxide is calcined 3h in air under 370 ℃, its granular size is adjusted to 0.27-0.75mm.Then, with dipping method Rh is loaded on the magnesium oxide.This product further in air in 370 ℃ of down calcinings, (Rh content is 2.6 * 10 to obtain the MgO catalyzer of load Rh
-3G/gMgO in molar weight, is 0.10mol%).By acetic acid rhodium (III) aqueous solution is added drop-wise among the burnt MgO bit by bit, rock after each drips and make it mixed adding, obtain above-mentioned impreg like this.The Rh concentration of acetic acid rhodium (III) aqueous solution is 1.7% (weight).The material that has flooded Rh in air in 120 ℃ of dry 2.5h, and under same atmosphere in 370 ℃ of calcining h down, obtain the MgO catalyzer (surface-area: 98m of load Rh
2/ g).Reaction embodiment 1
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 1 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream, and the Rh of oxidation state is converted into metal Rh.Then, handling mol ratio is CH
4: CO
2=1: 1 unstripped gas, temperature are 850 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 4,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 55% (CH under experiment condition
4Equilibrium conversion=55%), and at reaction beginning CH after 100 hours
4Transformation efficiency be 54%.Term " CH herein
4Transformation efficiency " be defined as following formula:
CH
4Transformation efficiency (%)=(A-B)/A * 100
A: CH in the raw material
4Mole number
B: CH in the product
4Mole number.Reaction embodiment 2
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 2 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: CO
2=1: 1 unstripped gas, temperature are 870 ℃, and pressure is 10kg/cm
2G, GHSV (is measurement basis with methane) is 2,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 71% (CH under experiment condition
4Equilibrium conversion=71%), and at reaction beginning CH after 50 hours
4Transformation efficiency be 71%.Reaction embodiment 3
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 3 is filled in the reactor, carries out the methane conversion experiment.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: CO
2: H
2O=1: 0.5: 1.0 unstripped gas, temperature are 850 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 4,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 61.5% (CH under experiment condition
4Equilibrium conversion=62.0%), and at reaction beginning CH after 400 hours
4Transformation efficiency be 61.0%.Reaction embodiment 4
The catalyzer (20cc) that will obtain in Preparation of Catalyst embodiment 4 is filled in the reactor, carries out the methane conversion experiment.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream, and the Rh of oxidation state is converted into metal Rh.Then, handling mol ratio is CH
4: CO
2: H
2O=1: 0.5: 1.0 unstripped gas, temperature are 850 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 3,500hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 61.0% (CH under experiment condition
4Equilibrium conversion=62.0%), and at reaction beginning CH after 280 hours
4Transformation efficiency be 61.0%.Reaction embodiment 5
The catalyzer (20cc) that will obtain in Preparation of Catalyst embodiment 5 is filled in the reactor, carries out the experiment that water makes methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: H
2O=1: 2 unstripped gas, temperature are 850 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 2,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency and the H of product gas
2/ CO mol ratio is respectively 72.0% (CH under experiment condition
4Equilibrium conversion=71%) and 4.6, and at reaction beginning CH after 280 hours
4Transformation efficiency be 71.8%.Reaction embodiment 6
The catalyzer (20cc) that will obtain in Preparation of Catalyst embodiment 6 is filled in the reactor, carries out the experiment that water makes methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: H
2O=1: 1 unstripped gas, temperature are 850 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 5,500hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency and the H of product gas
2/ CO mol ratio is respectively 52.2% (CH under experiment condition
4Equilibrium conversion=52.3%) and 3.8, and at reaction beginning CH after 250 hours
4Transformation efficiency be 52.0%.Reaction embodiment 7
The catalyzer (20cc) that will obtain in Preparation of Catalyst embodiment 7 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 920 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: CO
2=1: 1 unstripped gas, temperature are 850 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 4,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 54.0% (CH under experiment condition
4Equilibrium conversion=55%), and at reaction beginning CH after 380 hours
4Transformation efficiency be 53.5%.Reaction embodiment 8
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 8 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream, and the Rh of oxidation state is converted into metal Rh.Then, handling mol ratio is CH
4: CO
2=1: 1 unstripped gas, temperature are 850 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 4,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 55% (CH under experiment condition
4Equilibrium conversion=55%), and at reaction beginning CH after 320 hours
4Transformation efficiency be 54%.Reaction embodiment 9
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 9 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: CO
2=1: 1 unstripped gas, temperature are 870 ℃, and pressure is 10kg/cm
2G, GHSV (is measurement basis with methane) is 6,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 71% (CH under experiment condition
4Equilibrium conversion=71%), and at reaction beginning CH after 520 hours
4Transformation efficiency be 71%.Reaction embodiment 10
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 10 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: CO
2=1: 1 unstripped gas, temperature are 830 ℃, and pressure is 5kg/cm
2G, GHSV (is measurement basis with methane) is 2,500hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 73% (CH under experiment condition
4Equilibrium conversion=73%), and at reaction beginning CH after 100 hours
4Transformation efficiency be 71%.Reaction embodiment 11
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 11 is filled in the reactor, carries out the methane conversion experiment.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: CO
2: H
2O=1: 0.5: 0.5 unstripped gas, temperature are 880 ℃, and pressure is 10kg/cm
2G, GHSV (is measurement basis with methane) is 3,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 70% (CH under experiment condition
4Equilibrium conversion=70%), and at reaction beginning CH after 120 hours
4Transformation efficiency be 67%.Reaction embodiment 12
Repeat embodiment 8 in the same way, but be to use steam to replace carbonic acid gas.Reaction beginning CH after 5 hours and 320 hours
4Transformation efficiency be respectively 52% and 51%.Reaction embodiment 13
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 17 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream, and the Rh of oxidation state is converted into metal Rh.Then, handling mol ratio is CH
4: CO
2=1: 3 unstripped gas, temperature are 850 ℃, and pressure is 25kg/cm
2G, GHSV (is measurement basis with methane) is 6,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 86.1% (CH under experiment condition
4Equilibrium conversion=86.1%), the CO/H of product gas
2Mol ratio is 2.2.CH after reaction begins 280 hours
4Transformation efficiency be 85.7%.Reaction embodiment 14
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 7 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: CO
2=1: 5 unstripped gas, temperature are 830 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 5,500hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 95.7% (CH under experiment condition
4Equilibrium conversion=95.8%), the CO/H of product gas
2Mol ratio is 3.2.CH after reaction begins 400 hours
4Transformation efficiency be 95.4%.Reaction embodiment 15
The catalyzer (5cc) that will obtain in Preparation of Catalyst embodiment 9 is filled in the reactor, carries out making with carbonic acid gas the experiment of methane conversion.
Catalyzer reduces in 900 ℃ and to handle 1h in advance under hydrogen stream.Then, handling mol ratio is CH
4: CO
2=1: 1 unstripped gas, temperature are 800 ℃, and pressure is 20kg/cm
2G, GHSV (is measurement basis with methane) is 4,000hr
-1Reaction beginning CH after 5 hours
4Transformation efficiency be 45.5% (CH under experiment condition
4Equilibrium conversion=45.5%), the CO/H of product gas
2Mol ratio is 1.6.CH after reaction begins 150 hours
4Transformation efficiency be 45.2%.Reaction comparative example 1
As the same manner that reacts described in the embodiment 1 carries out making with carbonic acid gas the experiment of methane conversion, only is to use the catalyzer (5cc) of preparation among the comparison Preparation of Catalyst embodiment 1.In this example, reaction beginning CH after 5 hours and 15 hours
4Transformation efficiency be respectively 40% and 8%.Reaction comparative example 2
As react the same manner H described in the embodiment 6
2O makes the experiment of methane conversion, only is to use the catalyzer of preparation among the comparison Preparation of Catalyst embodiment 1.In this example, reaction beginning CH after 5 hours and 20 hours
4Transformation efficiency be respectively 45% and 10%.Reaction comparative example 3
As react the experiment that the same manner described in the embodiment 15 repeats to make with carbonic acid gas methane conversion, only be to use the 5cc catalyzer that obtains among the comparison Preparation of Catalyst embodiment 1.Reaction beginning CH after 5 hours
4Transformation efficiency be 42.0% (CH under experiment condition
4Equilibrium conversion=45.5%), the CO/H of product gas
2Mol ratio is 1.7.CH after reaction begins 15 hours
4Transformation efficiency be 5.0%.
Employed catalyzer demonstrates the carbon laydown activity that extremely suppresses among the present invention, has kept making the carbon containing organic compound to be converted into the desired activity of synthetic gas simultaneously.So according to the present invention, can be with good productive rate, long period prepares synthetic gas continuously, prevents carbon laydown simultaneously.
In addition, use catalyzer of the present invention,, can use small-scale device to prepare synthetic gas like this, thereby can reduce installation cost even under high pressure also can effectively suppress carbon laydown.
Claims (6)
1. method for preparing synthetic gas, wherein in the presence of a kind of catalyzer, make carbon containing organic compound and steam and/or carbon dioxide reaction, it is characterized in that described catalyzer comprises the carrier that is formed by metal oxide, and selected from rhodium, ruthenium, iridium, in palladium and the platinum at least load on catalytic metal on the described carrier in the lump, the specific surface area of described catalyzer is 25m
2/ g or littler, the electronegativity of the metal ion of described carrier metal oxide is 13.0 or lower, and the amount of described catalytic metal based on described carrier metal oxide, is 0.0005-0.1 mole % in metal.
2. the process of claim 1 wherein that described catalytic metal is rhodium and/or ruthenium.
3. claim 1 or 2 method, the electronegativity of the metal ion of wherein said carrier metal oxide is 4-12.
4. any one method of claim 1-3, the specific surface area of wherein said catalyzer is 0.01-10m
2/ g.
5. any one method of claim 1-4, wherein said metal oxide carrier is a magnesium oxide.
6. any one method of claim 1-5, wherein said carbon containing organic compound is a methane.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11043697 | 1997-04-11 | ||
| JP110436/1997 | 1997-04-11 | ||
| JP12630497 | 1997-04-30 | ||
| JP126304/1997 | 1997-04-30 | ||
| JP250062/1997 | 1997-08-29 | ||
| JP25006297 | 1997-08-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1254323A true CN1254323A (en) | 2000-05-24 |
| CN1121346C CN1121346C (en) | 2003-09-17 |
Family
ID=27311739
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98804035A Expired - Lifetime CN1121346C (en) | 1997-04-11 | 1998-04-13 | Process for preparation of synthesis gas |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US6312660B1 (en) |
| EP (1) | EP0974551B1 (en) |
| JP (1) | JP3345783B2 (en) |
| CN (1) | CN1121346C (en) |
| AT (1) | ATE273239T1 (en) |
| AU (1) | AU737644B2 (en) |
| CA (1) | CA2285974C (en) |
| DE (1) | DE69825577T2 (en) |
| ID (1) | ID29301A (en) |
| MY (1) | MY128194A (en) |
| NO (1) | NO331374B1 (en) |
| RU (1) | RU2201392C2 (en) |
| WO (1) | WO1998046524A1 (en) |
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- 1998-04-11 MY MYPI98001617A patent/MY128194A/en unknown
- 1998-04-13 US US09/254,635 patent/US6312660B1/en not_active Expired - Lifetime
- 1998-04-13 EP EP98912782A patent/EP0974551B1/en not_active Expired - Lifetime
- 1998-04-13 CA CA002285974A patent/CA2285974C/en not_active Expired - Lifetime
- 1998-04-13 RU RU99123630/12A patent/RU2201392C2/en active
- 1998-04-13 AU AU67492/98A patent/AU737644B2/en not_active Expired
- 1998-04-13 WO PCT/JP1998/001687 patent/WO1998046524A1/en active IP Right Grant
- 1998-04-13 DE DE69825577T patent/DE69825577T2/en not_active Expired - Lifetime
- 1998-04-13 AT AT98912782T patent/ATE273239T1/en not_active IP Right Cessation
- 1998-04-13 CN CN98804035A patent/CN1121346C/en not_active Expired - Lifetime
- 1998-04-13 ID IDW991365A patent/ID29301A/en unknown
- 1998-04-13 JP JP54372998A patent/JP3345783B2/en not_active Expired - Lifetime
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107847911A (en) * | 2016-06-10 | 2018-03-27 | 千代田化工建设株式会社 | Synthesis gas manufactures carriers for catalysts and its manufacture method, synthesis gas manufacture catalyst and its manufacture method and the manufacture method of synthesis gas |
| US10376864B2 (en) | 2016-06-10 | 2019-08-13 | Chiyoda Corporation | Carrier for synthesis gas production catalyst, method of manufacturing the same, synthesis gas production catalyst, method of manufacturing the same and method of producing synthesis gas |
| CN107847911B (en) * | 2016-06-10 | 2019-08-16 | 千代田化工建设株式会社 | Synthesis gas manufactures the manufacturing method of carriers for catalysts and its manufacturing method, synthesis gas manufacture catalyst and its manufacturing method and synthesis gas |
| CN108620051A (en) * | 2017-03-15 | 2018-10-09 | 单岩崑 | A kind of preparation method and applications of alkaline-earth metal or lanthanide series metal M and the mixed oxide of aluminium oxide |
| WO2023030367A1 (en) * | 2021-09-01 | 2023-03-09 | 中国石油大学(北京) | Method for preparing synthesis gas with high carbon monoxide concentration |
| CN116273054A (en) * | 2023-03-24 | 2023-06-23 | 中国科学院上海高等研究院 | Catalyst for preparing synthetic gas by photo-thermal catalysis of methane and carbon dioxide reforming, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2201392C2 (en) | 2003-03-27 |
| CA2285974A1 (en) | 1998-10-22 |
| EP0974551A4 (en) | 2000-05-24 |
| AU737644B2 (en) | 2001-08-23 |
| NO994912D0 (en) | 1999-10-08 |
| JP3345783B2 (en) | 2002-11-18 |
| WO1998046524A1 (en) | 1998-10-22 |
| EP0974551A1 (en) | 2000-01-26 |
| NO331374B1 (en) | 2011-12-12 |
| AU6749298A (en) | 1998-11-11 |
| US6312660B1 (en) | 2001-11-06 |
| MY128194A (en) | 2007-01-31 |
| CN1121346C (en) | 2003-09-17 |
| NO994912L (en) | 1999-10-08 |
| DE69825577D1 (en) | 2004-09-16 |
| ATE273239T1 (en) | 2004-08-15 |
| EP0974551B1 (en) | 2004-08-11 |
| ID29301A (en) | 2001-08-16 |
| DE69825577T2 (en) | 2005-09-22 |
| CA2285974C (en) | 2004-11-02 |
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